EP1685174A1 - Procede pour realiser des prepolymeres contenant des groupes isocyanate - Google Patents

Procede pour realiser des prepolymeres contenant des groupes isocyanate

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Publication number
EP1685174A1
EP1685174A1 EP04791088A EP04791088A EP1685174A1 EP 1685174 A1 EP1685174 A1 EP 1685174A1 EP 04791088 A EP04791088 A EP 04791088A EP 04791088 A EP04791088 A EP 04791088A EP 1685174 A1 EP1685174 A1 EP 1685174A1
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EP
European Patent Office
Prior art keywords
catalysts
acid
compounds
diisocyanate
isocyanate groups
Prior art date
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Granted
Application number
EP04791088A
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German (de)
English (en)
Other versions
EP1685174B1 (fr
Inventor
Michael Wind
Martin Kreyenschmidt
Imbridt Murrar
Hans-Jürgen Reese
Heiko Urtel
Hauke Malz
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds

Definitions

  • the invention relates to a process for the preparation of prepolymers containing isocyanate groups with a low degree of polymerization and a narrow molecular weight distribution, which have a low content of monomeric diisocyanate.
  • Prepolymers with urethane groups and terminal isocyanate groups are important intermediates for the production of polyurethanes. They have been known for a long time and have been widely described in the literature.
  • oligomeric products are also formed in addition to the stoichiometric reaction product, since each intermediate product contains reactive NCO or OH groups, which in turn can react further with starting materials or other intermediates already formed.
  • the formation of such oligomeric polyurethanes is undesirable, for example, when defined A-B-A structures are to be built up from isocyanate and polyol.
  • Such defined structures have a positive effect on the property profile of foamed and compact elastomers, such as thermoplastic polyurethanes or cast elastomers.
  • the prepolymer viscosity generally increases with the degree of polymerization. Highly viscous prepolymers generally limit further processing, especially in 2-component systems, since the miscibility of isocyanate and polyol components is difficult.
  • the product distribution in the prepolymer is significantly influenced by the molar ratio of the starting materials to one another.
  • the addable groups must be present in equimolar amounts in order to achieve high molecular weights.
  • the result is broad molecular weight distributions with a low molar fraction of the individual fractions.
  • the product distribution can be calculated in the implementation of symmetrical diisocyanates and diols using a statistical approach, the so-called Flory distribution.
  • diisocyanate-free prepolymers with a narrow molecular weight distribution can be obtained even with a moderate stoichiometric excess of the isocyanate component, even without additional purification steps.
  • DE 10229519 A1 describes a process for the preparation of prepolymers containing isocyanate groups with a low content of monomeric diisocyanate without an additional work-up step, asymmetrical dusocyanates being used as the dusocyanates.
  • a ratio of NCO groups to OH groups of 1.1 to 2.0 is used.
  • the MDI prepolymers produced according to the teaching of DE 10229 519 A1 have a comparatively high viscosity, which indicates a significant proportion of high molecular weight fractions in the prepolymer.
  • WO 03/033562 describes binders for reactive 1-component hotmelt adhesives or solvent-based PUR adhesives based on 2,4'-MDI and polyols with a reduced monomeric diisocyanate content and reduced viscosity compared to a corresponding 4,4'-MDI formulation , Here too, a slight excess of diisocyanate is used, which leads to a high viscosity of the product.
  • DE 101 57488 describes the preparation of isocyanate prepolymers with a low monomeric polyisocyanate content of less than 2% by weight.
  • One of the feedstocks for the prepolymer is a monomer-free prepolymer, which is based on 4,4'-MD! was produced.
  • EP 1 253 159 describes the preparation of prepolymers containing isocyanate groups with a high content with the structure ABA, where A is a residue of a diisocyanate and B is the rest of a diol.
  • a number of customary and known diisocyanates are proposed as diisocyanates, no distinction being made between symmetrical and asymmetrical diisocyanates.
  • the prepolymers are produced without the use of catalysts with a very high equivalent excess of diisocyanates, in the case of TDI from 6: 1 to 10: 1, which then has to be removed in a complex manner in many applications of the prepolymers.
  • WO 01/40340 A2 describes the preparation of ABA prepolymers, TDI being used as the isocyanate. The monomeric excess of diisocyanate is removed by distillation in the presence of at least one inert solvent.
  • EP 1 249460 also describes prepolymers with A-B-A structures, but the content of 2,4'-MDI in the diisocanate used is at most 70%.
  • EP 0370408 describes prepolymers with a proportion of at least 85% perfect A-B-A, but alky-substituted TDI derivatives are used as isocyanate component A.
  • WO 03/46040 describes low-monomer prepolymers containing isocyanate groups, which are prepared by reacting both symmetrical and asymmetrical diisocyanates with diols.
  • conventional catalysts such as amines or organometallic catalysts, can be used in the production.
  • the object of the invention was to develop a process for the preparation of prepolymers containing isocyanate groups which have a low proportion of monomeric diisocyanate, preferably less than 0.1% by weight and in particular less than 0.05% by weight, a low degree of polymerization and a have narrow molecular weight distribution.
  • dusocyanates in particular 2,4-TDI, 2,4'-MDI and / or IPDI, as the dusocyanates, the reaction taking place in the presence of organometallic catalysts, then removing these organometallic catalysts from the reaction product or are deactivated and excess monomeric diisocyanate is subsequently separated off from the reaction product.
  • the invention accordingly essentially relates to a process for the preparation of prepolymers containing isocyanate groups by reacting
  • dusocyanates a) asymmetric dusocyanates and as catalysts c) organometallic catalysts are used and these organometallic catalysts are removed, blocked or deactivated before the monomeric dusocyanates are separated off.
  • the catalysts are usually blocked by adding a blocking agent.
  • the catalysts can be deactivated, for example, by chemical modifications such as hydrolysis or reduction.
  • the catalysts can be removed by filtration.
  • the catalysts can be homogeneous catalysts, heterogeneous catalysts or supported catalysts. In the supported catalysts, the homogeneous catalysts are applied to a support.
  • the catalysts are described in more detail below.
  • Asymmetric diisocyanates are understood to mean those whose isocyanate groups have different reactivities. 2,4-TDI, 2,4'-MDI and / or isophorone diisocyanate (IPDI) are preferably used as asymmetric diisocyanates. 2,4'-MDI is particularly preferred.
  • Asymmetric diisocyanates can also be used in a mixture with symmetrical diisocyanates or polymeric isocyanates, the proportion of the asymmetric diisocyanates in the mixture being greater than 30% by weight, preferably greater than 60% by weight and particularly preferably greater than 90% by weight ,
  • organometallic compounds as a catalyst leads to isocyanate prepolymers with a low degree of polymerization.
  • Suitable catalysts according to the invention are, for. B. organometallic compounds of the metals from groups IVA (Ge, Sn, Pb), VA (Sb, Bi), IVB (Ti, Zr, Hf), VB (V, Nb, Ta) or VIIIB (especially Fe, Co, Ni, Ru).
  • suitable ligands are carboxylic acid anions, alcoholates, enolates, thiolates, mercaptides and alkyl ligands. These ligands can also be used in the form of chelating systems.
  • complexes bismuth (III) tris (2-ethylhexanoate), iron (III) acetate or zirconium (IV) propylate may be mentioned as examples.
  • Particularly preferred catalysts in the context of the invention are organometallic compounds from the
  • Group of tin (IV) compounds These catalysts show a particularly high selectivity with regard to the conversion of the more reactive isocyanate group, especially when using 2,4'-MDI as the diisocyanate.
  • Specific compounds are: dimethyl, dibutyl and dioctyl tin dilaurate, bis (dodecyl mercaptide), tin bis (2-ethylhexyl thio glycolate), tin diacetate, tin maleate, tin bisthioglycerol; Octyl tin tris (2-ethyl hexyl thioglycolate) and bis (D-methoxycabonyl ethyl) tin dilaurate.
  • Organometallic Ti (IV) catalysts are also preferred.
  • Ti (IV) compounds tetraisopropyl titanium, tetra-tert-butyl orthotitanium, tetra (2-ethylhexyl) titanium and titanium bis (ethylacetoacetato) diisopropoxide.
  • Bismuth-organic compounds in particular in the form of their carboxylates, have also proven to be useful.
  • Bismuth (III) tris (2-ethylhexanoate) and laurate may be mentioned as examples. Mixtures of metal catalysts, especially those mentioned, can also be used.
  • the organometallic catalysts used according to the invention are preferably used in an amount in the range between 0.1 and 5000 ppm, preferably between 1 and 200 ppm and particularly preferably between 1 and 30 ppm based on the reaction mixture. At low concentrations, the effects of the catalysts are only weak. Excessive catalyst concentrations lead to the formation of undesirable by-products such as allophanates, isocyanate dimers or trimers or ureas. In individual cases, the optimal amount of catalyst can easily be determined by a few orientation tests. Since organometallic catalysts can have a disruptive effect on the removal of the monomeric diisocyanate, in particular by distillation, it is necessary to deactivate or separate them after the prepolymer synthesis. Under the increased thermal stress on the distillation, catalysts can also catalyze the urethane cleavage, which can lead to an undesirable increase in the degree of polymerization.
  • blocking agents are generally metal deactivators and act by complexing the metallic central atom of the organometallic catalyst.
  • Lewis acidic metal deactivators are 2- (2-benzimidazolyl) phenol, 3- (2-imidazolin-2-yl) -2-naphthol, 2- (2-benzoxazolyl) phenol, 4-diethylamino-2, 2'-dioxy-5-methylazobenzene, 3-methyl-4- (2-oxy-5-methylphenylazo) -1-phenyl-5-pyrazolone, tris (2-tert-butyl-4-thio (2'methyl -4'hydroxy-5 , tert-butyl) phenyl-5-methyl) phenyl phosphite, decamethylene dicarboxydisalicyloyl hydrazide, 3-salicyloylamino
  • R 1 and R 4 are, independently of one another, any organic radicals, such as a linear, branched or cyclic alkyl radical, a linear, branched or cyclic alkenyl radical, a linear, branched or cyclic hydroxyl, halogen, amino or thioalkyl radical.
  • R 2 and R 3 are independently of one another nothing or hydrogen.
  • ⁇ and X 4 are independent of each other nothing or oxygen.
  • X 2 and X are Lewis acidic substituents, for example a halogen, O, OH, NH 2 , NO 2 , SH.
  • Citric acid malic acid, tartaric acid, acetoacetic acid, 2-chloroacetoacetic acid, benzoylacetic acid, acetone dicarboxylic acid, dehydroacetic acid, 3-oxovaleric acid and malonic acid and the associated esters, for example in the form of their methyl or ethyl esters, may be mentioned as specific compounds.
  • esters are used as metal deactivators in which R or R are hydroxy-terminated alkyl radicals with an average molecular weight M w of 170 to 10,000 g mol "1 , in particular 170 to 450 g mol " 1 .
  • These polymeric blocking compounds are prepared by esterification of the pure carboxylic acids or by transesterification, for example of methyl and ethyl esters with polyols having an average molecular weight M w of 170 to 10,000 g mol "1 , in particular 170 to 450 g mol " 1 , and functionality between 1 and 4, in particular from 1.7 to 2.5.
  • the polyols mentioned are mostly addition products of lower alkylene oxides, in particular ethylene oxide and / or propylene oxide, onto H-functional starter substances.
  • polymeric metal deactivators are particularly suitable for the process according to the invention because they are not or only slightly volatile under the thermal load of the distillative removal of the monomeric diisocyanate and can therefore complex the organometallic catalyst effectively until the end of the distillation.
  • Blocking agents whose boiling point at the same pressure is higher than that of the isomers of MDI, whose boiling point at 0.1 bar is higher than 250 ° C., are particularly suitable.
  • the metal deactivator is preferably added to the isocyanate prepolymer immediately after its synthesis in a 10 to 10,000 times, preferably in a 10 to 50 times, molar excess, based on the amount of the metal catalyst used.
  • hydrazine derivatives of salicylaldehyde are used as metal deactivators, such as, for example, decamethylenedicarboxy-disalicyloylhydrazide and 3-salcyloylamino-1,2,4-triazole.
  • metal deactivators such as, for example, decamethylenedicarboxy-disalicyloylhydrazide and 3-salcyloylamino-1,2,4-triazole.
  • Examples of such structures are decamethylene dicarboxydisalicyloylhydrazide (ADK rod CDA 6 ® ) and 3-salicyloylamino-1, 2,4-triazole (ADK rod CDA 1 ® ).
  • Decamethylene dicarboxydisalicyloyl hydrazides are particularly preferred. It may be advantageous not to use a single metal deactivator, but rather mixtures of metal deactivators. Preference is given to mixtures which contain salicyloylamino-1, 2,4-triazole and / or decamethylenedicarboxydisalicyloylhydrazide, in particular those mixtures which contain decamethylenedicarboxydisalicyloylhydrazide.
  • organometallic catalysts are used which are applied to a support material. These are referred to below as supported catalysts.
  • the supported catalyst can easily be separated from the isocyanate prepolymer by filtration following the prepolymer synthesis.
  • porous carrier materials which can originate from the group of organic or inorganic materials as well as those from inorganic oxides are generally suitable.
  • Preferred carrier materials are carbon materials (for example activated carbons or carbon blacks), silicon carbide, aluminum oxide, zirconium dioxide, silicon dioxide, titanium dioxide, zeolites, vanadium oxide, tungsten oxide, alkaline earth metal oxides or carbonates, iron oxide, zinc oxide, magnesium oxide, aluminum phosphates, titanium silicates, mixed oxides, talc, clay and Mixtures of the same.
  • Solid paraffin and polymers of vinyl chloride, ethylene, propylene, styrene, of the acrylates, substituted derivatives of the polymers mentioned and copolymers thereof can also be used as carrier materials.
  • porous carbon supports which can be obtained from a large number of commercial suppliers, have proven to be particularly suitable.
  • the carbon carriers used according to the invention have a specific surface area of 0.5 to about 3000 m 2 / g (determination according to DIN 66 131), a pore volume in the range from 0.01 ml / g to 2 ml / g (determination according to DIN 66 134 and DIN 66 135).
  • Porous carbon supports with a specific surface area of 1 to 1000 m 2 / g are preferred. In particular, carbon supports with a specific surface area of 5 to 500 m 2 / g are preferred.
  • the carbon carriers can be pretreated by the usual methods before application of the catalytically active compound, such as acid activation, for example with nitric acid, phosphoric acid or formic acid, calcination or impregnation, for example with alkali salts.
  • acid activation for example with nitric acid, phosphoric acid or formic acid
  • calcination or impregnation for example with alkali salts.
  • the application of a catalyst to the support material is carried out according to the prior art. Between 0.5 and 40% by weight of the metal, based on the total weight of the catalyst, is applied to the support.
  • the supported catalysts particularly preferably contain between 1 and 20% by weight of the metal.
  • a solution with the desired amount of the organometallic compound is first prepared, into which the support material is then added. Evaporation of the solvent gives a heterogeneous catalyst with the corresponding amount of active composition on the support material.
  • a carbon support can be introduced with stirring into a solution of dibutyltin dilaurate in ethanol and the catalyst can be obtained by evaporating the ethanol and then drying it.
  • the supported catalysts are used in a concentration of 0.001 to 5% by weight, in particular 0.01 to 0.1% by weight, and particularly preferably between 0.1 and 0.5% by weight, based on the reaction mixture, used.
  • the homogeneous catalysts are removed from the reactive isocyanate prepolymer by adsorption materials.
  • adsorption materials are suitable for the adsorption that were also mentioned for the support of the organometallic catalysts.
  • the chemical deactivation of the catalyst represents a further, but not preferred embodiment of the invention.
  • Another, non-preferred embodiment is the use of Lewis acidic heterogeneous catalysts.
  • These heterogeneous catalysts can be metals, metal oxides or metal halides chemical groups 2, 3, 4, 5, 6, 8, 9, 10, 13, 14 and mixtures thereof.
  • the various methods described for deactivating the organometallic catalyst ie deactivating by means of blocking agents, supporting homogeneous catalysts or using Lewis acid catalysts with subsequent filtration, adsorbing the metal catalyst or chemically deactivating by hydrolysis or Reduction, can also be combined as desired.
  • compounds having at least two hydrogen atoms reactive with isocyanate groups for the preparation of the prepolymers, preference can be given to those which have at least two hydroxyl and / or amino groups in the molecule. In particular, these compounds have a molecular weight Mn between 60 and 10,000 g / mol.
  • the compounds having at least two hydrogen atoms reactive with isocyanate groups are particularly preferably selected from the group comprising polyhydric alcohols, polyether alcohols, polyester alcohols, polyether polyamines, hydroxyl group-containing polycarbonates, hydroxyl group-containing polyacetals and any mixtures of at least two of these compounds. Polyhydric alcohols and polyether alcohols and mixtures thereof are particularly preferred.
  • polyhydric alcohols examples include alkanediols having 2 to 10, preferably 2 to 6, carbon atoms and higher alcohols, such as glycerol, trimethylolpropane or pentaerythritol. Natural polyols such as castor oil can also be used.
  • the polyether alcohols preferably have a functionality in the range from 2 to 8. They are usually produced by addition of alkylene oxides, in particular ethylene oxide and / or propylene oxide, onto H-functional starter substances.
  • alkylene oxides can be used individually, in succession or as a mixture.
  • suitable starting substances are water, diols, triols, higher-functional alcohols, sugar alcohols, aliphatic or aromatic amines or amino alcohols.
  • Polyether alcohols with an average molecular weight between 500 and 3000 g / mol and an average OH functionality of 2 to 3 are particularly suitable.
  • Particularly preferred starting substances for the preparation of these polyether alcohols are propylene glycol and glycerin.
  • Preferred alkylene oxides are ethylene oxide and propylene oxide.
  • Polyester alcohols with an average molecular weight between 1000 and 3000 g / mol and an average OH functionality of 2 to 2.6 are also preferred. Polyester alcohols based on adipic acid are particularly preferred.
  • the prepolymers are prepared by reacting the polyisocyanates with the compounds having at least two hydrogen atoms reactive with isocyanate groups.
  • the reaction of the dusocyanates with the compounds having at least two hydrogen atoms reactive with isocyanate groups can be carried out continuously or batchwise in conventional reactors, for example known tubular or stirred tank reactors, if appropriate in the presence of inert solvents, i.e. Compounds which are not reactive towards the isocyanates and OH-functional compounds.
  • the selectivity of the urethane reaction of asymmetric isoeyanates is further increased.
  • inert solvents are acetone, dichloromethane, ethyl acetate or toluene.
  • the reaction can be carried out in the presence of inert solvents at lower temperatures.
  • the reaction is generally carried out in a temperature range between 0 and 100 C C, in particular between 20 and 40 ° C.
  • the mass fraction of solvent in the total batch is 5 to 60% by weight, in particular 20 to 50% by weight.
  • the ratio of isocyanate groups to groups reactive with isocyanate groups is generally in the range between 1: 1 and 10: 1, preferably between 1: 1 and 7: 1 and particularly preferably between 1: 1 and 5: 1.
  • a given excess of diisocyanate that is to say also with moderate excesses in the range from 1: 1 to 1: 3
  • products having a lower degree of polymerization and a narrower molecular weight distribution are obtained than in processes according to the prior art.
  • the unreacted diisocyanate must be removed from the prepolymer after the reaction. This can be done in the usual way, for example by distillation, preferably thin-film distillation, or particularly preferably by using at least one short-path evaporator, as described for example in WO 03/46040.
  • the amount of diisocyanate to be removed is also cyanates less than in prior art processes.
  • Prepolymers free of monomeric diisocyanate with a given degree of polymerization and a given molecular weight distribution and thus, for example, a given viscosity can thus, based on the prepolymer synthesis, with higher yield and, based on the removal of the excess monomeric diisocyanate, with increased throughput, ie overall with improved economy compared to Prior art methods can be produced.
  • the reactive isocyanate prepolymer thus obtained preferably contains 0.01 to 0.5% by weight, preferably 0.02 to 0.09% by weight, of monomeric diisocyanate.
  • the NCO content of the reactive isocyanate prepolymers according to the invention is 3 to 14% by weight, in particular 5 to 9% by weight.
  • the viscosity of the reactive isocyanate prepolymers according to the invention measured according to Brockfield (ISO 255), is 100 mPas to 100000 mPas, preferably 1000 mPas to 40,000 mPas, at 50 ° C.
  • the prepolymers according to the invention are furthermore distinguished by a narrow molecular weight distribution, a low degree of polymerization and a content of ABA structures of at least 80 area%, based on the prepolymer.
  • the area% was determined by means of gel permeation chromatography (GPC).
  • the prepolymers containing isocyanate groups and urethane groups according to the invention are usually used for the production of polyurethanes.
  • the prepolymers containing isocyanate groups and urethane groups are reacted with compounds which can react with isocyanate groups.
  • the compounds that can react with isocyanate groups are, for example, water, alcohols, amines or compounds with mercapto groups.
  • the polyurethanes can be foams, in particular assembly foams, coatings, adhesives, in particular hot melt adhesives, paints, and compact or cellular elastomers. When used as sealants or adhesives, curing to the finished polyurethane is carried out in the simplest case by exposure to atmospheric moisture.
  • the prepolymers according to the invention can preferably also be used for the production of polyurethane films, in particular those for the food sector.
  • Prepolymers based on 2,4'-MDI are particularly suitable for this, as well as for use as hotmelt adhesives, in particular hotmelt adhesives, coatings or seals.
  • the excess diphenylmethane diisocyanate was removed in a short path evaporator, and a monomer-free product was obtained with a residual free diisocyanate content of less than 0.1% by weight and an isocyanate content of approximately 8.8% by weight of NCO.
  • Residual monomer content and molecular weight distribution were determined by means of GPC analysis.
  • Table 1 Product distribution of the uncatalyzed prepolymer reaction by means of GPC analysis after removal of the monomeric isocyanate (indication of the area percentages). All percentages relate to the total amount of oligomeric 2: 1, 3: 2 and higher isocyanate: polyol adducts.
  • Table 2 Product distribution of the prepolymer reaction catalyzed with 20 ppm DBTL (see comparative example 1) by means of GPC analysis after removal of the monomeric isocyanate (indication of the area percentages).
  • Example 2 According to the invention - in the presence of different concentrations of dibutyltin dilaurate
  • Example 3 According to the invention - in the presence of various organometallic catalysts
  • Table 3 Product distribution of the prepolymer reaction catalyzed with 20 ppm organometallic catalyst (see comparative example 1) by means of GPC analysis (indication of the area percentages).
  • Example 4 According to the Invention - In the Presence of a Heterogeneous Catalyst
  • the procedure was as in Example 1, but with a fixed molar 2,4'-MDI: PPG450 ratio of 7: 1 0.015% by weight, based on the total amount of polyol and isocyanate components, of the heterogeneous DBTL- Activated carbon catalyst added to the 2,4'-MDI and removed from the reaction mixture by filtration after the prepolymer synthesis.
  • Table 4 Product distribution of the prepolymer reaction catalyzed with a heterogeneous DBTL activated carbon catalyst (see comparative example 1) by means of GPC analysis after removal of the monomeric isocyanate (indication of the area percentages).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP04791088A 2003-11-03 2004-10-30 Procede pour realiser des prepolymeres contenant des groupes isocyanate Not-in-force EP1685174B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10351530A DE10351530A1 (de) 2003-11-03 2003-11-03 Verfahren zur Herstellung von Isocyanatgruppen enthaltenden Prepolymeren
PCT/EP2004/012335 WO2005042604A1 (fr) 2003-11-03 2004-10-30 Procede pour realiser des prepolymeres contenant des groupes isocyanate

Publications (2)

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EP1685174A1 true EP1685174A1 (fr) 2006-08-02
EP1685174B1 EP1685174B1 (fr) 2012-04-04

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US (1) US20070060731A1 (fr)
EP (1) EP1685174B1 (fr)
JP (1) JP4479926B2 (fr)
KR (1) KR101132864B1 (fr)
CN (1) CN100494243C (fr)
AT (1) ATE552284T1 (fr)
DE (1) DE10351530A1 (fr)
WO (1) WO2005042604A1 (fr)

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DE102005035000A1 (de) * 2005-07-22 2007-01-25 Basf Ag Isocyanatgruppen enthaltende Prepolymere
DE102005048823A1 (de) * 2005-10-10 2007-04-12 Bayer Materialscience Ag Reaktivsysteme, deren Herstellung und Verwendung
DE102006005938A1 (de) * 2006-02-09 2007-08-16 Fachhochschule Münster Emissionsarme Polyurethane
EP2439219A1 (fr) * 2010-10-06 2012-04-11 Sika Technology AG Réduction de la part de monomères comprenant des groupes isocyanates dans des compositions de polyuréthane durcissant à l'humidité
JP5753998B2 (ja) * 2010-11-02 2015-07-22 国立大学法人三重大学 ウレタン硬化性組成物、その硬化体、キットおよび硬化体の製造方法
EP2450387A1 (fr) * 2010-11-08 2012-05-09 Bayer MaterialScience AG Formule photopolymère pour la fabrication de supports holographiques
US20130079485A1 (en) 2011-09-22 2013-03-28 Prc-Desoto International, Inc. Sulfur-containing polyureas and methods of use
JPWO2017014188A1 (ja) * 2015-07-17 2018-05-24 横浜ゴム株式会社 接着剤組成物及び接着剤組成物の製造方法
FR3057871B1 (fr) * 2016-10-20 2018-11-02 Coatex Compose urethane modificateur de rheologie
CN109135293B (zh) * 2017-06-28 2022-04-22 万华化学集团股份有限公司 一种动态硫化硅橡胶/热塑性聚氨酯弹性体及其制备方法
JP7247115B2 (ja) * 2017-06-30 2023-03-28 シーカ テクノロジー アクチェンゲゼルシャフト 調節可能なポットライフを有する２成分ポリウレタン組成物
FR3075206B1 (fr) * 2017-12-19 2020-07-24 Coatex Sas Agent epaississant et composition assouplissante
EP3530683A1 (fr) 2018-02-27 2019-08-28 Covestro Deutschland AG Procédé et système de production d'un polymère de polyuréthane au moyen d'un catalyseur supporté
EP4028441A1 (fr) 2019-09-12 2022-07-20 LANXESS Corporation Composition prépolymère à faible teneur en polyuréthane libre

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CN1878808A (zh) 2006-12-13
JP4479926B2 (ja) 2010-06-09
WO2005042604A1 (fr) 2005-05-12
JP2007510026A (ja) 2007-04-19
KR20060123247A (ko) 2006-12-01
US20070060731A1 (en) 2007-03-15
KR101132864B1 (ko) 2012-04-03
EP1685174B1 (fr) 2012-04-04
DE10351530A1 (de) 2005-06-16
ATE552284T1 (de) 2012-04-15
CN100494243C (zh) 2009-06-03

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